US5302738A - Chiral phosphines - Google Patents

Chiral phosphines Download PDF

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Publication number
US5302738A
US5302738A US07/949,878 US94987892A US5302738A US 5302738 A US5302738 A US 5302738A US 94987892 A US94987892 A US 94987892A US 5302738 A US5302738 A US 5302738A
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Prior art keywords
bis
diyl
phosphonic acid
solution
compound
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Joseph Foricher
Bernd Heiser
Rudolf Schmid
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F Hoffmann La Roche AG
Hoffmann La Roche Inc
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Hoffmann La Roche Inc
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Assigned to HOFFMANN-LA ROCHE INC. reassignment HOFFMANN-LA ROCHE INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: F. HOFFMANN-LA ROCHE AG.
Assigned to F.HOFFMANN-LA ROCHE AG reassignment F.HOFFMANN-LA ROCHE AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FORICHER, JOSEPH, HEISER, BERND, SCHMID, RUDOLF
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Assigned to HOFFMANN-LA ROCHE INC. reassignment HOFFMANN-LA ROCHE INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ROCHE VITAMINS INC.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5027—Polyphosphines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4025—Esters of poly(thio)phosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/42—Halides thereof

Definitions

  • the present invention is concerned with novel, racemic and optically active phosphorus compounds of the general formula ##STR2## wherein R signifies lower alkyl, lower alkoxy or protected hydroxy, R 1 signifies lower alkoxy, phenoxy, benzyloxy, chlorine or bromine, R 2 stands for lower alkyl or lower alkoxy and n represents the number 0, 1 or 2.
  • Lower alkyl groups especially come into consideration here as substituents.
  • protecting groups for the hydroxy group there come into consideration in the scope of the present invention especially the usual ether-forming groups such as e.g. benzyl, allyl, benzyloxymethyl, lower alkoxymethyl, 2-methoxyethoxymethyl and the like.
  • the phosphorus compounds of formula I can be present not only in racemic form, but also in optically active form. Of those compounds of formula I in which R represents lower alkyl the optically active compounds are preferred.
  • Preferred compounds of formula I are, moreover, those in which n stands for the number 0, R 1 signifies phenoxy, ethoxy or chlorine and R represents methoxy, methoxymethyl or methyl, especially methoxy.
  • the compounds of formula I in accordance with the invention can be manufactured, for example, by subjecting a compound of the formula ##STR3## wherein R, R 2 and n have the above significance and R 3 signifies lower alkoxy, phenoxy or benzyloxy, to an Ullmann coupling, if desired resolving a thus-obtained compound of the formula ##STR4## wherein R, R 2 , R 3 and n have the above significance, which is present in the (RS) form into the (R) form and (S) form using dibenzoyltartaric acid or di-p-toluyltartaric acid and, if desired, replacing a lower alkoxy group denoted by R 3 in a racemic or optically active compound of formula III by chlorine or bromine.
  • the conversion of a compound of formula II into a compound of formula III which is present in the (RS) form is effected in accordance with the invention by means of an Ullmann coupling.
  • This is a reaction which is known per se and which can be carried out under the conditions which are usual for this.
  • this reaction can be carried out, for example, by heating a compound of formula II in an inert organic solvent such as e.g. N,N-dimethylformamide with e.g. copper powder activated with iodine to a temperature of about 110° C. to about 200° C.
  • the reaction can also be carried out in the absence of a solvent, i.e. in the melt.
  • R is different from lower alkyl, they can be prepared, for example, by subjecting a compound of the general formula ##STR5## wherein R 2 , R 3 and n have the above significance and R 4 signifies lower alkoxy or protected hydroxy, to an otho-lithiation/iodination reaction.
  • the ortho-lithiation of a compound of formula IV can be effected in a manner known per se.
  • this reaction can be effected by reacting a compound of formula IV with a lithium amide, e.g. lithium diisopropylamide or lithium 2,2,6,6-tetramethylpiperidine, in tetrahydrofuran at a temperature below 0° C., preferably at about -50° C. to about -78° C.
  • the subsequent iodination can be effected conveniently with molecular iodine, with ICl or IBr, likewise in tetrahydrofuran and likewise at a temperature below -50° C.
  • This is conveniently effected by the generally known reduction of the nitro group to the amino group, e.g. by means of hydrogen in the presence of a catalyst such as, for example, Pd/C, and subsequent diazotization/iodination in a manner known per se.
  • a catalyst such as, for example, Pd/C
  • the compounds of formulae IV and V which are also used as starting materials are known compounds or analogues of known compounds which can be prepared readily in a manner known per se; compounds IV e.g. in accordance with J. J. Monagle et al., J. Org. Chem. 32, 2477 (1967) and compounds V e.g. in accordance with K. S. Petrakis et al., J. Am. Chem. Soc. 1987, 109, 2831.
  • racemate resolution of a compound of III which is present in the (RS) form by means of (-)- or (+)-O,O'-dibenzoyltartaric acid (DBT) or (-)- or (+)-O,O'-di-p-toluyltartaric acid (DTT) can be carried out in an analogous manner to the racemate resolution of phosphine oxides, although this actually was unexpected having regard to the state of the art. This is conveniently effected in an inert organic solvent and at a temperature of about 0° C. to about 60° C.
  • solvents there can be mentioned here especially chloroform, methylene chloride, ethyl acetate, isopropyl acetate, acetone, alcohols such as methanol or ethanol and the like, as well as mixtures thereof.
  • R 3 signifies lower alkoxy in a racemic or optically active compound of formula III
  • this can be replaced by chlorine or bromine.
  • This substitution can be effected in a manner known per se, for example by reaction with thionyl chloride, thionyl bromide or phosphorus pentachloride in an inert organic solvent.
  • those compounds of formula III in which R represents lower alkyl can be obtained starting from compounds of the formula ##STR7## wherein R 2 and n have the above significance and R' represent lower alkyl.
  • a tert. amine such as, for example, triethylamine
  • a catalyst such as e.g. Pd(P-(phenyl) 3 ) 4
  • a catalyst such as e.g. PdCl 2 or NiCl 2 .
  • Compounds of formula I are valuable intermediates in the manufacture of not only known, but also novel diphosphine ligands. Furthermore, these are valuable building bricks of complexes with transition metals, especially with metals of Group VIII such as, for example, ruthenium, rhodium or iridium, which serve as catalysts in, inter alia, asymmetric hydrogenations.
  • transition metals especially with metals of Group VIII such as, for example, ruthenium, rhodium or iridium, which serve as catalysts in, inter alia, asymmetric hydrogenations.
  • the compounds of formula I can be converted readily into the mentioned diphosphine ligands. In this case it must only be taken into consideration that, when compounds of formula I in which R 1 signifies lower alkoxy are used, the lower alkoxy group is preferably firstly replaced by chlorine or bromine.
  • X represent chlorine, bromine or iodine, whereby there is obtained a compound of the formula ##STR9## wherein R, R 2 and n have the foregoing significance and R 5 signifies, for example, phenyl, substituted phenyl or ⁇ -furyl, which is subsequently reduced to a diphosphine ligand of the formula ##STR10## wherein R, R 2 , n and R 5 have the foregoing significance.
  • the compounds of formula VIII are known or novel diphosphine ligands.
  • reaction of a compound of formula I with R 5 MgX or R 5 Li can be effected in a manner known per se. Preferably, this is effected e.g. under the usual conditions of a Grignard reaction.
  • compounds of formula I in which R 1 represents phenoxy are reacted with a compound of the formula R 5 MgX and those in which R 1 represents chlorine or bromine are reacted with a compound of the formula R 5 -Li or R 5 MgX.
  • the reduction of a racemic compound of formula VII or of a compound of formula VII which is present in (R) or (S) form can be carried out in a manner known per se. This can be effected, for example, with silanes such as e.g. trichlorosilane in an aromatic hydrocarbon such as, for example, in boiling xylene or in acetonitrile etc., conveniently in the presence of an auxiliary base such as, for example, triethylamine or preferably tributylamine. If desired, this reduction can also be carried out in an autoclave under pressure.
  • silanes such as e.g. trichlorosilane in an aromatic hydrocarbon such as, for example, in boiling xylene or in acetonitrile etc.
  • an auxiliary base such as, for example, triethylamine or preferably tributylamine.
  • this reduction can also be carried out in an autoclave under pressure.
  • racemate resolution can be carried out in manner known per se, e.g. in accordance with the method described by S. Otsuka et al., in J. Am. Chem. Soc. 1971, 93, 4301.
  • the cooled reaction mixture was transferred into a round flask with methylene chloride and evaporated to dryness at 70° on a rotary evaporator.
  • the residue was treated with 200 ml of methylene chloride, the mixture was stirred well and filtered, and the filter residue was washed with 100 ml of methylene chloride.
  • the filtrate was washed three times with 100 ml of sat. NH 4 Cl solution, whereby a small amount of solid formed was filtered off in the first wash operation, and subsequently dried over MgSO 4 , filtered and concentrated.
  • the mother liquors and wash solutions were placed on one side in order to obtain the other enantiomer.
  • the butyllithium solution was dropped into the reaction vessel within about 10 minutes, whereby the temperature rose to about -50° and a white precipitate formed.
  • the CO 2 /acetone cooling bath was replaced by an ice/ethanol bath and the reaction mixture was stirred at about -15° for a further 30 minutes, then again cooled to -78°.
  • reaction mixture was treated with 150 ml of a solution of 100 g of sodium thiosulphate pentahydrate in 200 ml of deionized water, stirrer vigorously and subsequently treated with 100 ml of sat. NaHCO 3 solution.
  • the two-phase system was filtered in order to remove the precipitate formed and the phases were separated.
  • the aqueous phase was re-extracted once with 250 ml of ethyl acetate and the combined organic phases were washed with 250 ml of sat. NaCl solution, dried over MgSO 4 and evaporated.
  • the residue was taken up in 500 ml of ethyl acetate and the solution was washed three times with 250 ml of deionized water and with 250 ml of sat. NaCl solution, dried over MgSO 4 , filtered and concentrated.
  • the residue (118 g of yellow oil) was taken up in 170 ml of toluene and the solution was treated with 115 ml of hexane, whereby a white precipitate separated. This was removed by filtration and the filtrate was applied to a column of 450 g of silica gel.
  • the (2-iodo-3-methylphenyl)phosphonic acid diethyl ester used as the starting material was prepared as follows:
  • the mixture was treated with 10 ml of ether and the two-phase system was stirred at 0° to room temperature for a further 2 hours.
  • the mixture was treated with a small amount of Na 2 S 2 O 3 and with ether and H 2 O, the phases were separated and the organic phase was washed with 2N HCl, H 2 O, sat. NaHCO 3 solution and sat. NaCl solution, dried over Na 2 SO 4 , filtered and evaporated.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
US07/949,878 1991-03-15 1992-03-12 Chiral phosphines Expired - Lifetime US5302738A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH794/91 1991-03-15
CH79491 1991-03-15
PCT/CH1992/000050 WO1992016535A1 (de) 1991-03-15 1992-03-12 Diphosphonsaure derivate als zwischenprodukte in der herstellung von diphosphinliganden

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US (1) US5302738A (de)
EP (1) EP0530335B1 (de)
JP (1) JP3204668B2 (de)
AT (1) ATE141278T1 (de)
DE (1) DE59206900D1 (de)
DK (1) DK0530335T3 (de)
WO (1) WO1992016535A1 (de)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5516944A (en) * 1993-10-08 1996-05-14 Hoffmann-La Roche Inc. Optically active phosphorous compounds
US5686616A (en) * 1995-03-14 1997-11-11 Takasago International Corporation Process for preparing an optically active amine
US5739360A (en) * 1995-09-22 1998-04-14 Bayer Aktiengesellschaft Intermediates for the synthesis of bisphosphine compounds
US6037479A (en) * 1997-07-02 2000-03-14 Hoffman-La Roche Inc. Chiral diarsine compounds
US6162929A (en) * 1997-12-23 2000-12-19 Hoffmann-La Roche Inc. Process for the manufacture of bisphosphine oxide and bisphosphonate compounds
US6489513B2 (en) 2000-11-14 2002-12-03 Bayer Aktiengesellschaft Process for the preparation of enantiomerically pure (5, 5′-dichloro-6,6′-dimethoxy-biphenyl-2,2′-diyl)- bis(diphenylphosphine oxides)
US7094725B2 (en) 2003-07-11 2006-08-22 The Hong Kong Polytechnic University Biphenyldiphosphine compounds
US20070232653A1 (en) * 2006-04-03 2007-10-04 Stephan Bachmann Process for the preparation of enantiomerically enriched cyclic beta-aryl or heteroaryl carbocyclic acids
US20080027249A1 (en) * 2006-07-27 2008-01-31 Kurt Puentener Asymmetric hydrogenation of 1,1,1- trifluoroacetone
US20100152462A1 (en) * 2008-12-16 2010-06-17 Fabienne Hoffmann-Emery Process for the preparation of pyrollidine-3-carboxylic acids
US8288541B2 (en) 2007-08-13 2012-10-16 Hoffmann-La Roche Inc. Piperazine amide derivatives
US9062085B2 (en) 2010-09-10 2015-06-23 Kanata Chemical Technologies Inc. Biaryl diphosphine ligands, intermediates of the same and their use in asymmetric catalysis
WO2018189107A1 (en) 2017-04-11 2018-10-18 Dsm Ip Assets B.V. A new chiral biphenyl diphosphine ligand and process for preparation thereof

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE179981T1 (de) * 1992-01-31 1999-05-15 Hoffmann La Roche Diphosphinliganden
US5777087A (en) * 1996-04-18 1998-07-07 Celanese International Corporation Aryl diphosphines and catalysts containing the same
US20060008876A1 (en) 2004-07-07 2006-01-12 Shami A S E ME-5, ME-2, and EPP2: human protein antigens reactive with autoantibodies present in the serum of women suffering from endometriosis
US20110040091A1 (en) 2009-08-13 2011-02-17 Stephan Bachmann Process for the preparation of (r)-2-phenyl propionic acid derivatives
US20110054174A1 (en) 2009-08-28 2011-03-03 Stephan Bachmann Process for the preparation of a glucokinase activator compound

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE398132C (de) * 1922-05-14 1924-07-04 Rudolf Reinery Kaltmutternpresse
FR2140659A1 (de) * 1971-06-10 1973-01-19 Stauffer Chemical Co
US4495111A (en) * 1981-08-26 1985-01-22 Ato Chimie Hemiesters of phosphonic acids
US4556740A (en) * 1982-08-27 1985-12-03 Hoffmann-La Roche Inc. Phosphorus compounds
US4876269A (en) * 1986-09-10 1989-10-24 E. I. Du Pont De Nemours And Company Benoz-fused cycloalkane trans-1,2-diamine derivatives
US4952598A (en) * 1985-08-22 1990-08-28 Hoechst Aktiengesellschaft 3-phenyl indolinone derivatives, processes for their preparation, medicaments containing them, and their use
US5223632A (en) * 1990-03-01 1993-06-29 Takasago International Corporation 2,2'-bis(di-(3,5-dialkylphenyl)phosphino)-1,1'-binaphthyl and transition metal complex containing the samd ligand

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE128140T1 (de) * 1989-05-18 1995-10-15 Hoffmann La Roche Phosphorverbindungen.

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE398132C (de) * 1922-05-14 1924-07-04 Rudolf Reinery Kaltmutternpresse
FR2140659A1 (de) * 1971-06-10 1973-01-19 Stauffer Chemical Co
US3897491A (en) * 1971-06-10 1975-07-29 Stauffer Chemical Co Process for preparing alkyl or aryl phosphorus halides and mixed isomers thereof
US4495111A (en) * 1981-08-26 1985-01-22 Ato Chimie Hemiesters of phosphonic acids
US4556740A (en) * 1982-08-27 1985-12-03 Hoffmann-La Roche Inc. Phosphorus compounds
US4952598A (en) * 1985-08-22 1990-08-28 Hoechst Aktiengesellschaft 3-phenyl indolinone derivatives, processes for their preparation, medicaments containing them, and their use
US4876269A (en) * 1986-09-10 1989-10-24 E. I. Du Pont De Nemours And Company Benoz-fused cycloalkane trans-1,2-diamine derivatives
US5223632A (en) * 1990-03-01 1993-06-29 Takasago International Corporation 2,2'-bis(di-(3,5-dialkylphenyl)phosphino)-1,1'-binaphthyl and transition metal complex containing the samd ligand

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Greene, T. W. Protective Groups in Organic Synthesis ; John Wiley and Sons: New York, 1981, pp. 10, 14 16. *
Greene, T. W. Protective Groups in Organic Synthesis; John Wiley and Sons: New York, 1981, pp. 10, 14-16.

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5516944A (en) * 1993-10-08 1996-05-14 Hoffmann-La Roche Inc. Optically active phosphorous compounds
US5686616A (en) * 1995-03-14 1997-11-11 Takasago International Corporation Process for preparing an optically active amine
US5739360A (en) * 1995-09-22 1998-04-14 Bayer Aktiengesellschaft Intermediates for the synthesis of bisphosphine compounds
US6037479A (en) * 1997-07-02 2000-03-14 Hoffman-La Roche Inc. Chiral diarsine compounds
US6162929A (en) * 1997-12-23 2000-12-19 Hoffmann-La Roche Inc. Process for the manufacture of bisphosphine oxide and bisphosphonate compounds
US6489513B2 (en) 2000-11-14 2002-12-03 Bayer Aktiengesellschaft Process for the preparation of enantiomerically pure (5, 5′-dichloro-6,6′-dimethoxy-biphenyl-2,2′-diyl)- bis(diphenylphosphine oxides)
US7094725B2 (en) 2003-07-11 2006-08-22 The Hong Kong Polytechnic University Biphenyldiphosphine compounds
US20110105758A1 (en) * 2006-04-03 2011-05-05 Stephan Bachmann Process for the preparation of enantiomerically enriched cyclic beta-aryl or heteroarylcarbocyclic acids
US20070232653A1 (en) * 2006-04-03 2007-10-04 Stephan Bachmann Process for the preparation of enantiomerically enriched cyclic beta-aryl or heteroaryl carbocyclic acids
US20080027249A1 (en) * 2006-07-27 2008-01-31 Kurt Puentener Asymmetric hydrogenation of 1,1,1- trifluoroacetone
US7504544B2 (en) 2006-07-27 2009-03-17 Hoffmann-La Roche Inc. Asymmetric hydrogenation of 1,1,1-trifluoroacetone
US8288541B2 (en) 2007-08-13 2012-10-16 Hoffmann-La Roche Inc. Piperazine amide derivatives
US20100152462A1 (en) * 2008-12-16 2010-06-17 Fabienne Hoffmann-Emery Process for the preparation of pyrollidine-3-carboxylic acids
US8344161B2 (en) 2008-12-16 2013-01-01 Hoffmann-La Roche Inc. Process for the preparation of pyrollidine-3-carboxylic acids
US9062085B2 (en) 2010-09-10 2015-06-23 Kanata Chemical Technologies Inc. Biaryl diphosphine ligands, intermediates of the same and their use in asymmetric catalysis
WO2018189107A1 (en) 2017-04-11 2018-10-18 Dsm Ip Assets B.V. A new chiral biphenyl diphosphine ligand and process for preparation thereof

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Publication number Publication date
DE59206900D1 (de) 1996-09-19
EP0530335B1 (de) 1996-08-14
ATE141278T1 (de) 1996-08-15
DK0530335T3 (da) 1996-10-14
JP3204668B2 (ja) 2001-09-04
JPH05507503A (ja) 1993-10-28
WO1992016535A1 (de) 1992-10-01
EP0530335A1 (de) 1993-03-10

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